EP3231788A1 - Verfahren zur herstellung eines multifunktionalen produkts und vorrichtung zur anwendung des besagten verfahrens - Google Patents

Verfahren zur herstellung eines multifunktionalen produkts und vorrichtung zur anwendung des besagten verfahrens Download PDF

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EP3231788A1
EP3231788A1 EP17165960.0A EP17165960A EP3231788A1 EP 3231788 A1 EP3231788 A1 EP 3231788A1 EP 17165960 A EP17165960 A EP 17165960A EP 3231788 A1 EP3231788 A1 EP 3231788A1
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reactor
products
reactions
phase
multifunctional product
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EP3231788B1 (de
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Mario Araya Brenes
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Blueplasma Power SL
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Blueplasma Power SL
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C07C27/04—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds
    • C07C27/06—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds by hydrogenation of oxides of carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00026—Controlling or regulating the heat exchange system
    • B01J2208/00035—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2208/00044—Temperature measurement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00539—Pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00548—Flow
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention comprises: A) a process for obtaining a multifunctional product from raw material comprising oxygen, a synthesis gas and an optional additive, B) a device for applying the intended process, comprising at least three reactors in sequence wherein a maximum of four and a minimum of three groups of reactions occur, and C) the product finally obtained through this process.
  • the raw material that is introduced into a first reactor comprises a synthesis gas that mainly contains carbon monoxide and hydrogen
  • the raw material that is introduced into a second reactor comprises mainly oxygen
  • the raw material that is introduced into a third reactor comprises an optional additive, and these are exposed to catalysts under an atmosphere at medium temperature and pressure, so that three or four groups of chemical reactions occur that, after extracting most of the water generated as a residue during the process, produces as a result a multifunctional liquid product that may be used as a solvent, a foaming agent or an oxygenated fuel
  • said product normally a fluid, comprises polyoxymethylene dimethyl ethers with molecular formula CH3O(CH2O)nCH3 wherein n has a value between 1 and 7.
  • the fraction that corresponds to its byproducts may be reduced via a fractional distillation and its chemical stability may also be improved by modifying its pH by incorporating optional additive in the last group of reactions.
  • the cheapest conventional systems for converting the synthesis gas into a product with similar features to those of the multifunctional product of this patent are via the by-products of the synthesis gas itself: via methanol and formaldehyde or via dimethyl ether and formaldehyde.
  • the first route for producing a product similar to the multifunctional product of this patent requires first converting the synthesis gas to methanol at pressures of approximately 60 bar and temperatures of approximately 250°C, passing it several times through the same reactor since the water generated in the process limits conversion of the synthesis gas to methanol. This modern process of producing low pressure methanol was developed in late 1960.
  • the methanol After producing the methanol, it must be processed in a separate reactor and at a pressure close to atmospheric pressure, so that it becomes dissociated into formaldehyde and hydrogen at a temperature of approximately 600°C using copper or silver as catalysts, or instead oxidized with air to convert it to formaldehyde and water at 280°C using a pressure close to the atmospheric pressure.
  • the formaldehyde produced is made to react with methanol, increasing the pressure of the latter to 20 bar at an approximate temperature of 250°C in a reactive distillation process, using ionic exchange resin as an acid catalyst and thus producing a product with similar features to the multifunctional product.
  • the methanol in order to convert it to formaldehyde, the methanol must be reheated, generally in the presence of an oxidizing agent such as air, oxygen, water or CO2 and a suitable catalyst.
  • an oxidizing agent such as air, oxygen, water or CO2 and a suitable catalyst.
  • Another known route for producing a similar product to the multifunctional product is from a synthesis gas and oxygen. It is less conventional than the first route but produces a majority conversion, and this is converting the synthesis gas directly to dimethyl ether at a temperature of close to 250°C and at medium pressure: from 20 to 40 bar, it is then stored in a container at moderate pressuring ambient temperature, where it is extracted in order to be combined with formaldehyde taken from a source that contains or generates it, in order to finally process both products, dimethyl ether and formaldehyde, by heating them to a temperature of approximately 180°C and subjecting them to a pressure of about 20 bar using ion exchange resin as a catalyst.
  • This process requires producing the formaldehyde, generally obtained from methanol, with the drawbacks indicated for the first route, or taking it from other products that already contain the aldehyde but are more expensive; or in the pure form, such as is the case for trioxane, paraformaldehyde and formaldehyde in solution with methanol or water; this last route for obtaining formaldehyde in order to produce polyoxyethylene dimethyl ether is used in the process developed by BASF and disclosed in US Patent no. 7,999,140 B2 .
  • the invention relates to a process for obtaining a multifunctional product from a raw material comprising oxygen, synthesis gas, and an optional additive, and also relates to the device for applying said process and also to the product finally obtained with said process.
  • the process is thus self-heating, without requiring external sources to provide more heat other than that used a single time to start the process, and with respect to electric power, its use is required to maintain constant the pressure of the synthesis gas.
  • the process comprises at least three groups of reactions and a maximum of four groups of reactions.
  • the device that is part of this patent comprises at least three reactors in sequence: a first reactor, that may comprise in turn a main reactor and an auxiliary reactor, in which at least one of the two first groups of reactions takes place, a second reactor in which the third group of reactions takes place, and a third reactor in which the fourth group of reactions takes place.
  • the raw material Before the start of the process itself, the raw material is primed to a temperature of between 200° and 300°C and to a pressure between 18 and 60 bar, preferably close to 40 bar, since the raw material is a gas comprising mainly:
  • the first reactor which comprises in turn the main reactor and optionally an auxiliary reactor, at least one of the first two groups of reactions described below occurs.
  • the synthesis gas consisting mainly of hydrogen and carbon monoxide enters the first reactor at a temperature of between 200 and 300°C and at a pressure between 20 and 60 bar, preferably 40 bar, and comes in contact with at least one catalyst.
  • the catalyst is for producing methanol
  • the preferred compound is based on CuO/ZnO/Al2O3, which we shall call C1, which accelerates the main reaction of the first group: CO+2H2 ⁇ CH3OH.
  • the catalyst is for producing dimethyl ether
  • the preferred compound is based on CuO/ZnO/Al2O3 and aluminum oxide, which we shall call C2 and which accelerates the main reaction of the second group: 3CO + 3H2 ⁇ CH3OCH3 + CO2.
  • the catalysts corresponding to each one of these two group of reactions can be arranged in sequence, either in parallel or both mixed in any proportion, and the following reaction takes place: 2CH3OH ⁇ CH3OCH3+H2O, and the residual water from this reaction is used as a raw material to form more hydrogen via the side reaction: CO+H2O ⁇ CO2+H2, thus avoiding having an excess of water among the reagents, which means reducing the main limiter in the conversion of the synthesis gas to dimethyl ether and methanol.
  • the first reagent may comprise a main reagent and an auxiliary one.
  • the two groups of reactions may take place separately such that each reactor, main or auxiliary, contains only one type of these two catalysts, and the main and auxiliary reactors may be arranged in sequence, alternating, in parallel or in combined arrangements.
  • this first reactor comprises a main reactor and an auxiliary reactor to carry out the two groups of reactions and both the main reactor and the auxiliary one contain catalysts C1 and C2 mixed together
  • these reactors, main and auxiliary may also be arranged in sequence, alternating, in parallel or in a combined manner.
  • the products resulting from the first phase enter the second reactor of the device, wherein oxygen is added and they come into contact with catalyst C3 which favors the production of formaldehyde via the partial oxidation of part of the dimethyl ether or the methanol, via the following reactions: CH3OH+1/2O2 ⁇ CH2O+H2O y CH3OCH3+O2 ⁇ CH2O+H2O; they also favor the reaction 2CH3OH ⁇ CH3OCH3+H2O, producing dimethyl ether as a minority product.
  • catalyst C3 which favors the production of formaldehyde via the partial oxidation of part of the dimethyl ether or the methanol, via the following reactions: CH3OH+1/2O2 ⁇ CH2O+H2O y CH3OCH3+O2 ⁇ CH2O+H2O; they also favor the reaction 2CH3OH ⁇ CH3OCH3+H2O, producing dimethyl ether as a minority product.
  • the preferred catalysts for these reactions are based on at least two metals or compounds of the group: aluminum oxide, molybdenum oxide, vanadium and iron.
  • the molecules of aldehyde are incorporated to the dimethyl ether molecules via aldol reactions in order to reinforce the aldehyde content of the formulation of the multifunctional product, via which process, in this product, its volatility, flashpoint, vapor pressure and energy content can be adjusted according to the specific needs of the market in which it will be sold.
  • the third reactor is where the main intermediate products, dimethyl ether and formaldehyde, together with any unconverted synthesis gas and some minority by-products, are subjected to reactive distillation and come in contact with at least one type of strongly acidic catalyst, where the preferred one is an ion exchange resin which we shall call C4.
  • the optional additive may be incorporated, preferably comprising an amine to alkalinize and modify the pH of the multifunctional product, in order to prevent the reversal of the reactions of this group and to permanently sensitize the multifunctional product to detonation when used in internal combustion engines.
  • the preferred one is ethylene diamine and the second preferred one is 2-dimethylaminoethylazide, and preferably this optional additive may be incorporated to the process diluted in at least one group of diluents of the following group: i) an alcohol with 1 to 4 carbon atoms doped with nitromethane and ii) dibutyl ether doped with propylene glycol monomethyl ether.
  • the multifunctional product in conjunction with part of the unconverted synthesis gas and minority by-products then exit the device so that they can be partially or totally separated by means of a fractional distillation.
  • this comprises preferably at least one amine wherein the preferred one is ethylenediamine and the second preferred one is 2-dimethylaminoethylazide.
  • this optional additive may be diluted in an alcohol with 1 to 4 carbon atoms doped with nitromethane and/or diluted in dibutyl ether doped with propylene glycol monomethyl ether in order to increase the sensitivity to detonation provided to the multifunctional product by the amine.
  • One of the characteristics of this process is that between the first and second phase the pressure of the products resulting from the first phase is reduced, preferably by two thirds, and the excess of pressure between the first and the second phase is used to increase the pressure of the products between the third and fourth phase.
  • the products from the first and second phase provide heat for the third reactor, to the raw materials entering the device or to the optional additive that enters the device via the additive injector.
  • the device has means to recover the heat and pressure.
  • the device comprises at least three reactors connected in sequence wherein at least three of the four groups of main reactions occur, so that it can be used continuously and allowing the intermediate products to pass from one to the other without requiring storage outside the process.
  • At least one first reactor which may comprise a main reactor and an auxiliary one, is for the first two groups of reactions; at least one second reactor is for the third group of reactions; and at least one third reactor is for the fourth group of reactions.
  • the first reactor contains at least one catalyst from amongst C1 and C2, the second reactor contains catalyst C3 and the third reactor contains catalyst C4.
  • All these reactors comprise a pipe bank within which the catalysts are found and through which the reagent products circulate.
  • the pipe bank for each reactor is covered by a jacket that rests on at least two seats, preferably four, and which may be disks/flanges.
  • the outer disks/flanges serve as covers for the reactor. Whereas between the inner disks/flanges and those serving as covers there are chambers that collect the products that enter or exit the pipe bank.
  • the outermost disks/flanges are used to introduce or extract from the process certain materials such as raw materials, oxygen, water, additives or the end product.
  • Each reactor comprises at least two chambers, preferably each one on opposite ends thereof, in which said chambers comprise orifices to receive or discharge mainly the reagents and orifices communicated with the inside to receive or discharge the products that circulate within the pipes in the reactor.
  • the second and third reactor our communicated with oxygen and additive injectors, respectively.
  • the pipes of the pipe bank for each reactor are fastened to the disks/flanges adjacent to the chambers, preferably via welding, pressure or threads, and said disks/flanges have a through orifice for each pipe of the pipe bank.
  • the device comprises a direct means and an indirect means for transferring the heat from the main groups of exothermic reactions to the group of endothermic reactions, which may happen at the same time.
  • the different means that the device has for transferring this heat from the exothermic reactions to the endothermic reactions may be direct, indirect or a combination of both.
  • the direct means is via recirculation of the product resulting from the exothermic reactions of the first, second and third group of reactions, through the conduct in which the endothermic reactions occur, directly causing the heat exchange and transferring it to the endothermic reactions via said resulting product.
  • the indirect means is via recirculation of the product resulting from the exothermic reactions of the first, second and third group of reactions, through the conduct in which the endothermic reactions occur, indirectly causing the heat exchange and transferring it to the endothermic reactions via a fluid that does not chemically participate in the process.
  • the multifunctional product resulting from application of the optional additive, when used in internal combustion engines, has the characteristic of having a pH above 7, making it an alkaline product that is highly sensitive to detonation, which factors are positive and differentiating for its use as a component in fuels for internal combustion engines.
  • Figure 1 shows a diagram of the process of the invention and the preferred catalysts that can be used, and should not be considered the only one but instead a mere descriptive example showing the device with a first reactor (1) comprising a main reactor (2) and an auxiliary reactor (3), a second reactor (4) and a third reactor (5).
  • the first group of reactions takes place in the main reactor (2) of the first reactor (1)
  • the second group of reactions takes place in the auxiliary reactor (3) of the first reactor (1)
  • the third group of reactions takes place in the second reactor (4)
  • the fourth group of reactions takes place in the third reactor (5).
  • An oxygen injector (8) is associated with the second reactor (4) and an injector of the optional additive (9) is associated with the third reactor (5).
  • the multifunctional product (11) and the unconverted synthesis gas and any minority by-products (12) are extracted from the process.
  • throttle/relief valves that are responsible for discharging any excess of product without affecting the environment and without the end production or quality of the multifunctional product being substantially affected.
  • interconnections are a first interconnection (15) located between the main reactor (2) and the second reactor (4) and a second interconnection (14) located between the auxiliary reactor (3) and the third reactor (5).
  • the synthesis gas is compressed to 40 bar with the compressor (6) and it is then heated to 280°C in the heat exchanger (7) in order to then enter the first reactor (1) via its main reactor (2) and its auxiliary reactor (3), which may be arranged in sequence or in parallel.
  • the synthesis gas enters in parallel to the main reactor (2) and the auxiliary reactor (3) of the first reactor (1).
  • These reactors house catalysts C1 and C2 respectively, and both work at 280°C and a pressure of 40 bar.
  • the main reactor (2) of the first reactor (1) takes place the first group of reactions to produce mainly the methanol, which then enters the auxiliary reactor (3) together with the gas that did not react and other by-products from the first group of reactions. All the products that circulate through the main reactor (2) enter the auxiliary reactor (3) that contains catalyst C2, with the gas that did not react in the main reactor (2) to produce mainly dimethyl ether via the second group of reactions.
  • the dimethyl ether and the methanol each in conjunction with their respective raw materials that did not react and the respective by-products derived from their respective reactions, such as carbon dioxide, methyl formate and carbonic acid, together with the oxygen and the optional additive injected from outside the device, all enter the second reactor (4) at the same temperature at which the products leave the auxiliary reactor (3) and at a reduced pressure so that, via the third group of reactions, the methanol may mainly be oxidized to formaldehyde, under the presence of catalyst C3.
  • the oxygen is injected by an oxygen injector (8) comprising an orifice that communicates the outside with the inside of the second reactor (4) as shown in figure 1 .
  • This third reactor produces, as well as the multifunctional product, a minority or traces of: water, methanol, carbonic acid, formic acid, acetic acid, carbon dioxide, methyl formate and formaldehyde; other products also exit in gas form, from the raw material that was not converted, such as carbon monoxide, methane, hydrogen, oxygen and hydrocarbon traces, which we shall call minority by-products (12).
  • the interconnections are a first interconnection (15) from the main reactor (2) to the second reactor (4) and a second interconnection (14) from the auxiliary reactor (3) to the third reactor (5)
  • the products from the first reactor (1) comprising its main (2) and auxiliary (3) reactors and from the second reactor (4) provide heat to the third reactor (5) indirectly via a non-volatile liquid that circulates between the jacket and the pipe bank containing the reactors, using a heat exchange and the excess heat can optionally be applied to the raw materials entering the device and to the optional additive that may enter the device via the additive injector (9).
  • the multifunctional product (11) that exits the third reactor (5) may be separated into its different components via a distillation, where fractional distillation is preferred.
  • the liquid or gas products that exit reactor R4 together with the polyoxymethylene dimethyl ethers, may optionally be recirculated and serve as a raw material for a gasification process for the production of synthesis gas.
  • the synthesis gas is compressed to 40 bar with the compressor (6) and is then heated to 280°C in the heat exchanger (7) to then enter the main reactor (2) and the auxiliary reactor (3) which may be arranged in sequence or in parallel, where in the main reactor this synthesis gas comes in contact with catalyst C1 and in the auxiliary reactor (3) it comes in contact with catalyst C2.
  • the end products of the main reactor and the auxiliary reactor are mainly methanol and dimethyl ether respectively, obtaining a weight conversion of more than 40% of the synthesis gas used.
  • gaseous by-products of the synthesis gas and part of the synthesis gas that did not react in the main (2) and auxiliary (3) reactors, mainly: hydrogen, carbon monoxide, carbon dioxide and nitrogen infiltrated with oxygen and raw materials.
  • the products of the main (2) and auxiliary (3) reactors both exit at 280°C and 34 bar of pressure, which is preferably reduced to 12 bar, and then enter the second reactor (4) that houses the catalyst C3 and either pure oxygen or a compound containing oxygen is added with an oxygen injector (8).
  • liquid by-products separated together with the other gas products that exit from the third reactor may optionally be used in the production process for synthesis gas, in preheating raw materials and optional additives.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP17165960.0A 2016-04-15 2017-04-11 Verfahren zur herstellung eines multifunktionalen produkts und vorrichtung zur anwendung des besagten verfahrens Active EP3231788B1 (de)

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CN109557964A (zh) * 2018-12-27 2019-04-02 南通江天化学股份有限公司 一种高浓度甲醛生产线的分布式控制系统
CN113365724A (zh) * 2019-01-30 2021-09-07 西门子能源全球有限两合公司 反应器级联和用于运行反应器级联的方法

Families Citing this family (2)

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US11643381B2 (en) 2021-07-08 2023-05-09 Hexion Inc. Processes for aldehyde synthesis
CN113582135B (zh) * 2021-09-13 2024-08-02 文亮 一种甲醛生产尾气制高纯氢气的装置及方法

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WO2000029364A1 (en) * 1998-11-12 2000-05-25 Bp Amoco Corporation Preparation of polyoxymethylene dimethyl ethers by reaction of dimethylether with formaldehyde over heterogeneous catalysts
US6166266A (en) * 1998-11-12 2000-12-26 Bp Amoco Corporation Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxidation of methanol
US6956134B2 (en) * 2004-01-08 2005-10-18 The Regents Of The University Of California Oxidation of methanol and/or dimethyl ether using supported molybdenum-containing heteropolyacid catalysts
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109557964A (zh) * 2018-12-27 2019-04-02 南通江天化学股份有限公司 一种高浓度甲醛生产线的分布式控制系统
CN109557964B (zh) * 2018-12-27 2020-09-29 南通江天化学股份有限公司 一种高浓度甲醛生产线的分布式控制系统
CN113365724A (zh) * 2019-01-30 2021-09-07 西门子能源全球有限两合公司 反应器级联和用于运行反应器级联的方法

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ES2637949A1 (es) 2017-10-18
BR102017007842A2 (pt) 2017-10-31
JP2018021006A (ja) 2018-02-08
EP3231788B1 (de) 2020-08-12
US20170297989A1 (en) 2017-10-19
JP6877226B2 (ja) 2021-05-26
BR102017007842B1 (pt) 2022-03-29
DK3231788T3 (da) 2020-11-16
ES2637949B1 (es) 2018-07-27
ES2831862T3 (es) 2021-06-09

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